Method to provide pipeline quality natural gas

ABSTRACT

The present invention relates to a method of separating and recovering NGLs from a natural gas feedstream. Specifically, the present method allows for the separation of ethane and heavier hydrocarbons and/or propane and heavier hydrocarbons from a raw natural gas feedstream to provide pipeline quality natural gas. One embodiment of this method provides for the use of a regenerable adsorbent media which is regenerated by a microwave heating system. Said regeneration step may be operated as a batch process, a semi-continuous process, or a continuous process.

FIELD OF THE INVENTION

This invention relates to a method for providing pipeline qualitynatural gas from a natural gas feedstream comprising natural gasliquids, preferably at or near the source of the natural gas feedstream,by separating and recovering natural gas liquids.

BACKGROUND OF THE INVENTION

Natural gas consists primarily of saturated hydrocarbon components suchas methane, ethane, propane, butane, and heavier hydrocarbons. Naturalgas typically contains about 60-100 mole percent methane, the balancebeing primarily heavier alkanes. Alkanes of increasing carbon number arenormally present in decreasing amounts. Carbon dioxide, hydrogensulfide, nitrogen, and other gases may also be present.

There are many reasons to separate the higher alkanes known as naturalgas liquids (NGL) from natural gas to provide a methane-rich natural gasstream. One such reason is to meet pipeline specifications or liquefiednatural gas (LNG) specification for heating value, dew point, andcondensation. Some stationary internal combustion engines, such asnatural gas engines, are designed to operate for optimal efficiencywithin a specific BTU range and may require higher maintenance costs,higher operating temperatures, reduced equipment life expectancy, and/orgenerate increased pollution if operated at higher BTUs.

Additionally, it may be financially desirable to recover natural gasliquids from natural gas. NGLs including ethane, propane, butane, andlesser amounts of other heavy hydrocarbons may be used as petrochemicalfeedstocks where they have a higher value as compared to their value asa fuel gas component.

In other instances, gas is co-produced with oil and the concentrationsof NGLs can be very high ranging from a fraction of a percent of the gasflow to tens of percent. This gas can be of poor quality due to highlevels of carbon dioxide, nitrogen, and other components. The gas flowrate can be small and often it is not economical to bring a pipeline toan isolated location where natural gas is produced, such gas issometimes referred to as stranded gas. In these instances, the bestalternative is to flare the gas. However, flaring of gas high in NGLsmay have a significant negative impact on the environment, accountingfor a significant amount of CO₂ and heat that is injected into theatmosphere. In addition to capturing value for separated NGLs that canbe stored in a tank for later transportation and sale, it would beenvironmentally advantageous to remove the NGLs from the gas to reducethe amount of CO₂ and heat uselessly released into the environment.

There are two basic steps for the separation of natural gas liquids froma natural gas stream. First, the liquids must be extracted from thenatural gas. Second, these natural gas liquids must be separatedthemselves, down to their base components. There are two principletechniques for removing NGLs from the natural gas stream are the oilabsorption method and the cryogenic expander process. These twoprocesses account for around 90 percent of total natural gas liquidsproduction.

The absorption method of NGL extraction utilizes an absorbing oil whichhas an affinity for NGLs. Before the oil has picked up any NGLs, it istermed “lean” absorption oil. As the natural gas is passed through anabsorption tower, it is brought into contact with the absorption oilwhich soaks up a high proportion of the NGLs. The “rich” absorption oil,now containing NGLs, exits the absorption tower through the bottom. Itis now a mixture of absorption oil, propane, butanes, pentanes, andother heavier hydrocarbons. The rich oil is fed into lean oil stills,where the mixture is heated to a temperature above the boiling point ofthe NGLs, but below that of the oil. This process allows for therecovery of around 75 percent of butanes, and 85 to 90 percent ofpentanes and heavier molecules from the natural gas stream.

Although there are many known adsorption processes, there is always acompromise between high recovery and process simplicity (i.e., lowcapital investment). Common adsorption technologies focus on removal ofhydrocarbons, which works well in non-hydrocarbon rich streams, but islimited in applicability in hydrocarbon continuous streams. Further thistechnology is not selective for certain molecular size/weight.

Cryogenic processes are also used to extract NGLs from natural gas.While absorption methods can extract almost all of the heavier NGLs, thelighter hydrocarbons, such as ethane, are often more difficult torecover from the natural gas stream. In certain instances, it iseconomic to simply leave the lighter NGLs in the natural gas stream.However, if it is economic to extract ethane and other lighterhydrocarbons, cryogenic processes are required for high recovery rates.Essentially, cryogenic processes consist of dropping the temperature ofthe gas stream to around −120 degrees Fahrenheit. There are a number ofdifferent ways of chilling the gas to these temperatures, but one of themost effective is known as the turbo expander process. In this process,external refrigerants are used to cool the natural gas stream. Then, anexpansion turbine is used to rapidly expand the chilled gases, whichcauses the temperature to drop significantly. This expansion can takeplace across a valve as well. This rapid temperature drop caused by theJoule-Thompson effect condenses ethane and other hydrocarbons in the gasstream, while maintaining methane in gaseous form. This process allowsfor the recovery of about 90 to 95 percent of the ethane originally inthe natural gas stream. In addition, the expansion turbine is able toconvert some of the energy released when the natural gas stream isexpanded into recompressing the gaseous methane effluent, thus savingenergy costs associated with extracting ethane. These plants can becalled JT plants, refrig plants, or cryo plants which are all variationson the same temperature drop processes.

While reliable, cryogenic systems suffer from a number of shortcomingsincluding high horsepower requirements. Further, such systems requirerelatively rigorous and expensive maintenance to function properly.Mechanical refrigeration systems also have practical limits with respectto the amount of cold that may be delivered, accordingly, the efficiencyand capacity of such systems is limited. The operating window (range ofoperating conditions the plants can function well within) is arelatively narrow window, requires time to start-up and shut-downeffectively, and is quite capitally intensive. As a result thesefacilities are often used at higher gas flow rates to ensure a moreeconomic cost to treat the system. And if the facility is to beconstructed, and can only operate in a narrow range of operatingconditions, there are significant upstream treatment systems required toremove CO₂ (amine systems), water (glycol dehydration) and sometimeseven pre-chilling (propane chillers).

Once NGLs have been removed from the natural gas stream, the mixedstream of different NGLs must be separated out. The process used toaccomplish this task is called fractionation. Fractionation works basedon the different boiling points of the different hydrocarbons in the NGLstream. Essentially, fractionation occurs in stages consisting of theboiling off of hydrocarbons one by one. By proceeding from the lightesthydrocarbons to the heaviest, it is possible to separate the differentNGLs reasonably easily.

Of the various alternative technologies, adsorption process appears tobe the most promising. An adsorbent suitable for the separation of NGLsshould have high adsorption capacity and selectivity for either olefinor paraffin. Adsorbed component should be able to desorb easily bysimple chemical engineering operation such as by increasing thetemperature or by reducing the pressure. Conventional adsorbents such aszeolites, activated carbon, activated alumina, silica gels, polymersupported silver chloride, copper-containing resins, and the like knownin the prior art which exhibit selectivity for ethylene or propylenesuffer from one or more drawbacks such as slow adsorption kinetics, pooradsorption capacity, and/or selectivity. Furthermore, due to everchanging business requirements and demands, it is desirable to haveadsorbents exhibiting even higher adsorption capacity, selectivity,and/or reversibility for efficient separation of hydrocarbon gases.

NGLs are valuable as separate products; therefore, it is profitable toremove them from raw natural gas feedstreams. NGLs have their own uniqueproperties that make them suited to a specific use—for example, butaneis used in lighters, while propane is used in backyard grills and homeheating systems. Petrochemical plants are the largest consumers of NGLs,particularly ethane, which is used in the manufacturing of plastics.Processing facilities remove NGLs so they can be recovered and usedseparately.

NGLs are primarily transported by pipeline under pressure in a liquidstate. Where NGLs pipelines do not exist, NGLs can be liquefied andtransported by truck, railcar, or ship.

It would be desirable to have a method, preferably an on-site method toremove some or all of the NGLs from a raw natural gas feedstreams toprovide pipeline quality natural gas suitable for transportationdirectly through the mainline transmission grid. Further, where the NGLpipelines exist, it would be desirable to transport the recovered NGLsas mixed NGLs to processing facilities, refineries and import terminalsto fractionation plants, petrochemical plants, export facilities andrefineries. Alternatively, it may be desirable to separate the NGLs,store, and deliver them as ethane, propane, butane, etc., topetrochemical plans or direct propane or butane customers along thepipeline systems and/or by pipeline, truck, rail, ship, or othersuitable means.

SUMMARY OF THE INVENTION

The present invention is such a method to remove and recover some or allof the natural gas liquids (NGLs) from a natural gas feedstreams toprovide pipeline quality natural gas and to capture value for therecovered NGLs.

In one embodiment, the present invention is a method to remove andrecover some or all of the natural gas liquids (NGLs): ethane, propane,butane, pentane, or heavier hydrocarbons, from a natural gas feedstream,preferably a natural gas feedstream from an oil well, a gas well, acondensate well, or a pipeline natural gas containing NGLs to provide amethane-rich natural gas supply for pipeline transportation and/or foruse as fuel for a combustion process, wherein the NGLs are separatedfrom the natural gas feedstream by means of a NGLs separation unitcomprising: (i) an adsorption unit comprising an adsorption bedcomprising an adsorbent media which adsorbs NGLs to form a loadedadsorbent media and (ii) a regeneration unit comprising a means toregenerate loaded adsorbent media by causing the release of adsorbedNGLs from the loaded adsorbing media and forming regenerated adsorbentmedia wherein the method further comprises the steps of: (a) passing thenatural gas feedstream through the adsorption unit generating theadsorbent loaded with NGLs and a methane-rich natural gas supply,preferably with a BTU level equal to or less than 1073, (b) transportingthe adsorbent loaded with NGLs from the adsorption unit to theregeneration unit, (c) regenerating the adsorbent loaded with NGLs byreleasing the adsorbed NGLs from the loaded adsorbing media and formingregenerated adsorbent media (d) transporting the regenerated adsorbentmedia back to the adsorption unit for reuse, (e) recovering the releasedNGLs, and (f) providing the methane-rich natural gas supply to a naturalgas pipeline for transportation.

In another embodiment of the present invention, the method describedherein above further comprises the step: (g) transporting the recoveredNGLs by pipeline, truck, rail, or ship to a chemical processing facilitywhere one or more of the NGLs is used as a chemical feedstock in thechemical processing facility.

In the method of the present invention described herein above,preferably the adsorption media is silica gel, alumina, silica-alumina,zeolites, activated carbon, polymer supported silver chloride,copper-containing resins, porous cross-linked polymeric adsorbents,pyrolized macroporous polymers, or mixtures thereof.

In the method of the present invention described herein above the loadedadsorption media is regenerated by means of reduced pressure over themedia, heating the media, or a combination of reduced pressure andheating and preferably regenerated by a microwave heating system,preferably the regeneration step is operated as a batch process, asemi-continuous process, or as a continuous process.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of a method of the present invention to providepipeline quality natural gas.

FIG. 2 is a schematic of a NGLs adsorption and regeneration processuseful for the method of the present invention.

FIG. 3 is a schematic of a NGLs adsorption and regeneration processuseful for the method of the present invention comprising a microwaveregeneration unit.

FIG. 4 shows the initial and repeat sorption isotherms for butane forExample 1.

FIG. 5 shows the initial and repeat sorption isotherms for butane forExample 2.

FIG. 6 shows the initial and repeat sorption isotherms for propane forExample 3.

FIG. 7 shows the sorption isotherms for methane, ethane, propane,butane, and pentane for Example 1.

FIG. 8 shows the sorption isotherms for methane, ethane, propane,butane, and pentane for Example 2.

FIG. 9 shows the sorption isotherms for methane, ethane, propane,butane, and pentane for Example 3 an example of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Raw natural gas comes from three types of wells: oil wells, gas wells,and condensate wells. Natural gas that comes from oil wells is typicallytermed “associated gas”. This gas can exist separate from oil in theformation (free gas), or dissolved in the crude oil (dissolved gas).Natural gas from gas and condensate wells, in which there is little orno crude oil, is termed “non-associated gas”. Gas wells typicallyproduce raw natural gas by itself, while condensate wells produce freenatural gas along with a semi-liquid hydrocarbon condensate. Whateverthe source of the natural gas, once separated from crude oil (ifpresent) it commonly exists as methane in mixtures with otherhydrocarbons; principally ethane, propane, butane, and pentanes and to alesser extent heavier hydrocarbons.

Raw natural gas often contain a significant amount of impurities, suchas water or acid gases, for example carbon dioxide (CO₂), hydrogensulfide (H₂S), sulfur dioxide (SO₂), carbon disulfide (CS₂), hydrogencyanide (HCN), carbonyl sulfide (COS), or mercaptans as impurities. Theterm “natural gas feedstream” as used in the method of the presentinvention includes any natural gas source, raw or raw natural gas thathas been treated one or more times to remove water and/or otherimpurities.

The terms “natural gas liquids” (NGL) and “ethane plus” (C₂+) referbroadly to hydrocarbons having two or more carbons such as ethane,propane, butane, and possibly small quantities of pentanes or heavierhydrocarbons. Preferably, NGL have a methane concentration of 5 molpercent or less.

The term “methane-rich” refers broadly to any vapor or liquid stream,e.g., after fractionation from which at least some ethane plus amountshave been recovered. Thus, a methane-rich stream has a higherconcentration of C₁ than the concentration of C₁ in associated andnon-associated natural gas. Preferably, the concentration increase of C₁is from removal of at least 90 mole percent of the ethane in the naturaland removal of at least 95 mole percent of the propane plus.

The present invention is a method to remove and recover some or allnatural gas liquids (NGLs) from natural gas or raw natural gas, producedin remote locations prior to transportation through a natural gaspipeline and/or from pipeline natural gas containing NGLs. The presentinvention provides several benefits. First, pipeline quality natural gasis provided by removing NGLs. Secondly, value for the recovered NGLs canbe captured as NGLs are valued chemical building blocks. NGLs havesignificantly higher value than natural gas or methane itself. RecoveredNGLs can be condensed, stored as necessary, and transported by pipeline,truck, rail, ship, or other means to a chemical processing facility thatuses NGLs, for example chemical manufacturers where they may be used aschemical feedstocks.

In another embodiment, some natural gas pipelines are operated with someNGLs present (referred to as pipeline natural gas containing NGLs). Suchpipeline natural gas containing NGLs may be used for combustionprocesses. In such cases, the NGLs are typically consumed as fuel insubsequent combustion processes. However, in some instances, thepipeline natural gas containing NGLs is delivered to a location that canuse NGLs to produce chemicals, such as refineries ethylene or propylenecrackers, or other types of processing facilities. In such instances,the pipeline natural gas containing NGLs may be a natural gas source forthe method of the present invention wherein the NGLs may be removed fromthe pipeline natural gas containing NGLs and subsequently transferred toa process where value is captured for the recovered NGLs beyond that ofthe NGLs fuel value. Such examples include chemical processes, includingbut not limited to ethylene cracking, propylene cracking, butanecracking, oil refining, propane dehydrogenation.

FIG. 1 shows a schematic of one embodiment of the present inventionwherein raw natural gas 3 from an oil well, a gas well, or a condensatewell is passed through a separation unit 90 to remove some or all of theNGLs 29 forming a methane-rich natural gas stream 5 that is passesthrough a compressor 100 and provided to a natural gas pipeline 120 fortransportation. The NGLs are discharged 29 from the separation unit 90and recovered individually or as a mixture of gases (e.g., as C₂, C₃,C₄, C₅, etc.) or liquefied and recovered individually or as a mixture ofliquids.

FIG. 2 shows a schematic of the separation unit 90 for the processdepicted in FIG. 1. The separation unit 90 comprises an adsorption unit10 comprising an adsorption bed 2 comprising an adsorbent media whichadsorbs NGLs to form a loaded adsorbent media and a regeneration unit 20comprising a means to regenerate loaded adsorbent media 32 causing therelease of adsorbed NGLs 33 from the loaded adsorbing media and formingregenerated adsorbent media which can be transported 8 back to theadsorption unit 10 for reuse.

Preferably, the methane-rich natural gas 5 suitable for pipelinetransmission preferably has a BTU value equal to or less than 1073, morepreferably equal to or less than 1066, more preferably equal to or lessthan 1058, and most preferably a BTU value of equal to or less than1028.

Preferably, the separation means 90 comprises an adsorbent. Suitableadsorbents are solids having a microscopic structure. The internalsurface of such adsorbents is preferably between 100 to 2000 m²/g, morepreferably between 500 to 1500 m²/g, and even more preferably 1000 to1300 m²/g. The nature of the internal surface of the adsorbent in theadsorbent bed is such that C₂ and heavier hydrocarbons are adsorbed.Suitable adsorbent media include materials based on silica, silica gel,alumina or silica-alumina, zeolites, activated carbon, polymer supportedsilver chloride, copper-containing resins. Most preferred adsorbentmedia is a porous cross-linked polymeric adsorbent or a partiallypyrolized macroporous polymer. Preferably, the internal surface of theadsorbent is non-polar.

In one embodiment, the present invention is the use of an adsorbentmedia to extract NGLs from a natural gas stream. The mechanism by whichthe macroporous polymeric adsorbent extracts the NGLs from the naturalgas stream is a combination of adsorption and absorption; the dominatingmechanism at least is believed to be adsorption. Accordingly, the terms“adsorption” and “adsorbent” are used throughout this specification,although this is done primarily for convenience. The invention is notconsidered to be limited to any particular mechanism.

When an adsorbent media has adsorbed any amount of C₂+ hydrocarbons itis referred to as “loaded”. Loaded includes a range of absorbance from alow level of hydrocarbons up to and including saturation with adsorbedhydrocarbons.

The term “macroporous” is used in the art interchangeably with“macroreticular,” and refers in general to pores with diameters of about500 Å or greater. “Mesopores” are characterized as pores of between 50 Åand larger but less than 500 Å. “Micropores” are characterized as poresof less than 50 Å. The engineered distribution of these types of poresgives rise to the desired properties of high adsorption capacity forNGLs and ease of desorption of NGLs under convenient/practical chemicalengineering process modifications (increase in temperature or reducedpressure [vacuum]). The process giving rise to the distribution ofmicropores, mesopores and macropores can be achieved in various ways,including forming the polymer in the presence of an inert diluent orother porogen to cause phase separation and formation of micropores bypost cross-linking.

In one embodiment, the adsorbent media of the present invention is amacroporous polymeric adsorbent of the present invention is a postcross-linked polymeric synthetic adsorbents engineered to have highsurface area, high pore volume and high adsorption capacities as well asan engineered distribution of macropores, mesopores and micropores.

Preferably, the macroporous polymeric adsorbent of the present inventionis hypercrosslinked and/or methylene bridged having the followingcharacteristics: a BET surface area of equal to or greater than 500 m²/gand preferably equal to or greater than 1,000 m²/g, and having aparticle size of 300 microns to 1500 microns, preferably 500 to 1200microns.

Examples of monomers that can be polymerized to form macroporouspolymeric adsorbents useful are styrene, alkylstyrenes, halostyrenes,haloalkylstyrenes, vinylphenols, vinylbenzyl alcohols, vinylbenzylhalides, and vinylnaphthalenes. Included among the substituted styrenesare ortho-, meta-, and para-substituted compounds. Specific examples arestyrene, vinyltoluene, ethylstyrene, t-butylstyrene, and vinyl benzylchloride, including ortho-, meta-, and para-isomers of any such monomerwhose molecular structure permits this type of isomerization. Furtherexamples of monomers are polyfunctional compounds. One preferred classis polyvinylidene compounds, examples of which are divinylbenzene,trivinylbenzene, ethylene glycol dimethacrylate, divinylsulfide anddivinylpyridine. Preferred polyvinylidene compounds are di- and trivinylaromatic compounds. Polyfunctional compounds can also be used ascrosslinkers for the monomers of the first group.

One preferred method of preparing the polymeric adsorbent is by swellingthe polymer with a swelling agent, then crosslinking the polymer in theswollen state, either as the sole crosslinking reaction or as inaddition to crosslinking performed prior to swelling. When a swellingagent is used, any pre-swelling crosslinking reaction will be performedwith sufficient crosslinker to cause the polymer to swell when contactedwith the swelling agent rather than to dissolve in the agent. The degreeof crosslinking, regardless of the stage at which it is performed, willalso affect the porosity of the polymer, and can be varied to achieve aparticular porosity. Given these variations, the proportion ofcrosslinker can vary widely, and the invention is not restricted toparticular ranges. Accordingly, the crosslinker can range from about0.25% of the polymer to about 45%. Best results are generally obtainedwith about 0.75% to about 8% crosslinker relative to the polymer, theremaining (noncrosslinking) monomer constituting from about 92% to about99.25% (all percentages are by weight).

Other macroporous polymeric adsorbents useful in the practice of thisinvention are copolymers of one or more monoaromatic monomers with oneor more nonaromatic monovinylidene monomers. Examples of the latter aremethyl acrylate, methyl methacrylate and methylethyl acrylate. Whenpresent, these nonaromatic monomers preferably constitute less thanabout 30% by weight of the copolymer.

The macroporous polymeric adsorbent is prepared by conventionaltechniques, examples of which are disclosed in various United Statespatents. Examples are U.S. Pat. Nos. 4,297,220; 4,382,124; 4,564,644;5,079,274; 5,288,307; 4,950,332; and 4,965,083. The disclosures of eachof these patents are incorporated herein by reference in their entirety.

For polymers that are swollen and then crosslinked in the swollen state,the crosslinking subsequent to swelling can be achieved in a variety ofways, which are further disclosed in the patents cited above. One methodis to first haloalkylate the polymer, and then swell it and crosslink byreacting the haloalkyl moieties with aromatic groups on neighboringchains to form an alkyl bridge. Haloalkylation is achieved byconventional means, an example of which is to first swell the polymerunder non-reactive conditions with the haloalkylating agent whileincluding a Friedel-Crafts catalyst dissolved in the haloalkylatingagent. Once the polymer is swollen, the temperature is raised to areactive level and maintained until the desired degree of haloalkylationhas occurred. Examples of haloalkylating agents are chloromethyl methylether, bromomethyl methyl ether, and a mixture of formaldehyde andhydrochloric acid. After haloalkylation, the polymer is swelled furtherby contact with an inert swelling agent. Examples are dichloroethane,chlorobenzene, dichlorobenzene, ethylene dichloride, methylene chloride,propylene dichloride, and nitrobenzene. A Friedel-Crafts catalyst can bedissolved in the swelling agent as well, since the catalyst will be usedin the subsequent crosslinking reaction. The temperature is then raisedto a level ranging from about 60° C. to about 85° C. in the presence ofthe catalyst, and the bridging reaction proceeds. Once the bridgingreaction is complete, the swelling agent is removed by solventextraction, washing, drying, or a combination of these procedures.

The pore size distribution and related properties of the finishedadsorbent can vary widely and no particular ranges are critical to theinvention. In most applications, best results will be obtained at aporosity (total pore volume) within the range of from 0.5 to 1.5 cc/g ofthe polymer. A preferred range is 0.7 to 1.3 cc/g. Within these ranges,the amount contributed by macropores (i.e., pores having diameters of500 Å or greater) will preferably range from 0.025 to 0.6 cc/g, and mostpreferably from 0.04 to 0.5 cc/g. The surface area of the polymer, asmeasured by nitrogen adsorption methods such as the well-known BETmethod, will in most applications be within the range of 150 to 2100m²/g, and preferably from 400 to 1400 m²/g. The average pore diameterwill most often range from 10 Å to about 100 Å.

The form of the macroporous polymeric adsorbent is likewise not criticaland can be any form which is capable of containment and contact with aflowing compressed air stream. Granular particles and beads arepreferred, ranging in size from about 50 to about 5,000 microns, with arange of about 500 to about 3,000 microns particularly preferred.Contact with the adsorbent can be achieved by conventional flowconfigurations of the gas, such as those typically used in fluidizedbeds or packed beds. The adsorbent can also be enclosed in a cartridgefor easy removal and replacement and a more controlled gas flow pathsuch as radial flow.

The macroporous polymeric adsorbent can function effectively under awide range of operating conditions. The temperature will preferably bewithin any range which does not cause further condensation of vapors orany change in physical or chemical form of the adsorbent. Preferredoperating temperatures are within the range of from 5° C. to 75° C., andmost preferably from 10° C. to 50° C. In general, operation at ambienttemperature or between ambient temperature and 10° C. to 15° C. aboveambient will provide satisfactory results. The pressure of the naturalgas stream entering the adsorbent bed can vary widely as well,preferably extending from 2 psig (115 kPa) to 1000 psig (7000 kPa). Thepressure will generally be dictated by the plant unit where the productgas will be used. A typical pressure range is from 100 psig (795 kPa) to300 psig (2170 kPa). The residence time of the natural gas stream in theadsorbent bed will most often range from 0.02 second to 5 seconds, andpreferably from 0.3 second to 3.0 seconds. The space velocity of thenatural gas stream through the bed will most often fall within the rangeof 0.1 foot per second to 5 feet per second, with a range of 0.3 footper second to 3 feet per second preferred. Finally, the relativehumidity can have any value up to 100%, although for convenience, thepreferred range of relative humidity is about 25% to about 98%.

The macroporous polymeric adsorbents of the present invention describedherein above can be used to separate ethane, propane, butane, pentane,and heavier hydrocarbons from mixed gases containing methane.Preferably, the macroporous polymeric adsorbents of the presentinvention adsorb equal to or greater than 60 cm³ STP of propane per gramof sorbent at 35° C. and 500 mmHg of propane. Preferably, the adsorbentsof the present invention adsorb equal to or greater than 60 cm³ STP ofn-butane per gram of sorbent at 35° C. and 100 mmHg of n-butane.Furthermore, these materials are able to be degassed of propane orn-butane and then able to reabsorb equal to or greater than 60 cm³ STPof propane per gram of sorbent at 35° C. and 500 mmHg of propane orreabsorb greater than 60 cm³ STP of n-butane per gram of sorbent at 35°C. and 100 mmHg of n-butane at least once. Preferably, the adsorbents ofthe present invention adsorb equal to or greater than 30 cm³ STP ofethane per gram of sorbent at 35° C. and 600 mmHg of ethane. Preferably,the adsorbents of the present invention adsorb equal to or greater than100 cm³ STP of pentane per gram of sorbent at 35° C. and 50 mmHg ofpentane.

In another embodiment, the adsorbent media of the present invention is apyrolized macroporous polymeric adsorbent media to extract NGLs from anatural gas stream.

Pyrolized macroporous polymeric adsorbent media are well known, forinstance see U.S. Pat. No. 4,040,990, incorporated by reference hereinin its entirety. Partially pyrolyzed particles, preferably in the formof beads or spheres, produced by the controlled decomposition of asynthetic polymer of specific initial porosity. In a preferredembodiment, the pyrolyzed particles are derived from the thermaldecomposition of macroreticular ion exchange resins containing amacroporous structure.

In general pyrolysis comprises subjecting the starting polymer tocontrolled temperatures for controlled periods of time under certainambient conditions. The primary purpose of pyrolysis is thermaldegradation while efficiently removing the volatile products produced.

The maximum temperatures may range from about 300° C. to up to about900° C., depending on the polymer to be treated and the desiredcomposition of the final pyrolyzed particles. Higher temperature, e.g.,about 700° C. and higher result in extensive degradation of the polymerwith the formation of molecular sieve sized pores in the product.

Most desirably, thermal decomposition (alternatively denoted “pyrolysis”or “heat treatment”) is conducted in an inert atmosphere comprised of,for example, argon, neon, helium, nitrogen, or the like, using beads ofmacroreticular synthetic polymer substituted with a carbon-fixing moietywhich permits the polymer to char without fusing in order to retain themacroreticular structure and give a high yield of carbon. Among thesuitable carbon-fixing moieties are sulfonate, carboxyl, amine, halogen,oxygen, sulfonate salts, carboxylate salts and quaternary amine salts.These groups are introduced into the starting polymer by well-knownconventional techniques, such as those reactions used to functionalizepolymers for production of ion exchange resins. Carbon-fixing moietiesmay also be produced by imbibing a reactive precursor thereof into thepores of macroreticular polymer which thereupon, or during heating,chemically binds carbon-fixing moieties onto the polymer. Examples ofthese latter reactive precursors include sulfuric acid, oxidizingagents, nitric acid, Lewis acids, acrylic acid, and the like.

Suitable temperatures for practicing the process of this invention aregenerally within the range of 300° C. to about 900° C., although highertemperatures may be suitable depending upon the polymer to be treatedand the desired composition of the final pyrolyzed product. Attemperatures above about 700° C. the starting polymer degradesextensively with the formation of molecular sieve sized pores in theproduct, i.e., 4 Å to 6 Å critical dimensions, yielding a preferredclass of adsorbents according to this invention. At lower temperatures,the thermally-formed pores usually range from 6 Å to as high as 50 Å inaverage critical size. A preferred range of pyrolysis temperatures isbetween about 400° C. and 800° C. As will be explained more fullyhereinafter, temperature control is essential to yield a partiallypyrolyzed material having the composition, surface area, pore structuresand other physical characteristics of the desired product. The durationof thermal treatment is relatively unimportant, providing a minimumexposure time to the elevated temperature is allowed.

A wide range of pyrolyzed resins may be produced by varying the porosityand/or chemical composition of the starting polymer and also by varyingthe conditions of thermal decomposition. In general, the pyrolyzedresins of the invention have a carbon to hydrogen ratio of 1.5:1 to20:1, preferably 2.0:1 to 10:1, whereas activated carbon normally has aC/H ratio much higher, at least greater than 30:1 (Carbon and GraphiteHandbook, Charles L. Mantell, Interscience Publishers, N.Y. 1968, p.198). The product particles contain at least 85% by weight of carbonwith the remainder being principally hydrogen, alkali metals, alkalineearth metals, nitrogen, oxygen, sulfur, chlorine, etc., derived from thepolymer or the functional group (carbon-fixing moiety) contained thereonand hydrogen, oxygen, sulfur, nitrogen, alkali metals, transitionmetals, alkaline earth metals and other elements introduced into thepolymer pores as components of a filler (may serve as a catalyst and/orcarbon-fixing moiety or have some other functional purpose).

The pore structure of the final product must contain at least twodistinct sets of pores of differing average size, i.e., multimodal poredistribution. The larger pores originate from the macroporous resinousstarting material which preferably contains macropores ranging frombetween about 50 to about 100,000 Å in average critical dimension. Thesmaller pores, as mentioned previously, generally range in size from 4 Åto 50 Å, depending largely upon the maximum temperature duringpyrolysis. Such multimodal pore distribution is considered a novel andessential characteristic of the composition of the invention.

The pyrolyzed polymers of the invention have relatively large surfacearea resulting from the macroporosity of the starting material and thesmaller pores developed during pyrolysis. In general the overall surfacearea as measured by nitrogen adsorption ranges between about 50 and 1500m²/gram. Of this, the macropores will normally contribute 6 to 700m²/gram, preferably 6 to 200 m²/g, as calculated by mercury intrusiontechniques, with the remainder contributed by the thermal treatment.Pore-free polymers, such as “gel” type resins which have been subjectedto thermal treatment in the prior art do not contribute the large poresessential to the adsorbents of the invention nor do they perform withthe efficiency of the pyrolyzed polymers described herein.

The duration of pyrolysis depends upon the time needed to remove thevolatiles from the particular polymer and the heat transfercharacteristics of the method selected. In general, the pyrolysis isvery rapid when the heat transfer is rapid, e.g., in an oven where ashallow bed of material is pyrolyzed, or in a fluidized bed. To preventburning of the pyrolyzed polymer, normally the temperature of thepolymer is reduced to not more than 400° C., preferably not more than300° C., before the pyrolyzed material is exposed to air. The mostdesirable method of operation involves rapid heating to the maximumtemperature, holding the temperature at the maximum for a short periodof time (in the order of 0 to 20 minutes) and thereafter quicklyreducing the temperature to room temperature before exposing the sampleto air. Products according to the invention have been produced by thispreferred method by heating to 800° C. and cooling in a period of 20 to30 minutes. Longer holding periods at the elevated temperatures are alsosatisfactory, since no additional decomposition appears to occur unlessthe temperature is increased.

Activating gases such as CO₂, NH₃, O₂, H₂O or combinations thereof insmall amounts tend to react with the polymer during pyrolysis andthereby increase the surface area of the final material. Such gases areoptional and may be used to obtain special characteristics of theadsorbents.

The starting polymers which may be used to produce the pyrolyzed resinsof the invention include macroreticular homopolymers or copolymers ofone or more monoethylenically or polyethylenically unsaturated monomersor monomers which may be reacted by condensation to yield macroreticularpolymers and copolymers. The macroreticular resins used as precursors inthe formation of macroreticular heat treated polymers are not claimed asnew compositions of matter in themselves. Any of the known materials ofthis type with an appropriate carbon-fixing moiety is suitable. Thepreferred monomers are those aliphatic and aromatic materials which areethylenically unsaturated.

Examples of suitable monoethylenically unsaturated monomers that may beused in making the granular macroreticular resin include: esters ofacrylic and methacrylic acid such as methyl, ethyl, 2-chloroethyl,propyl, isobutyl, isopropyl, butyl, tert-butyl, sec-butyl, ethylhexyl,amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl, isobornyl, benzyl,phenyl, alkylphenyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,propoxymethyl, propoxyethyl, propoxypropyl, ethoxyphenyl, ethoxybenzyl,ethoxycyclohexul, hydroxyethyl, hydroxypropyl, ethylene, propylene,isobutylene, diisobutylene, styrene, ethylvinylbenzene, vinyltoluene,vinylbenzylchloride, vinyl chloride, vinyl acetate, vinylidene chloride,dicyclopentadiene, acrylonitrile, methacrylonitrile, acrylamide,methacrylamide, diacetone acrylamide, functional monomers such asvinylbenzene, sulfonic acid, vinyl esters, including vinyl acetate,vinyl propionate, vinyl butyrate, vinyl laurate, vinyl ketones includingvinyl methyl ketone, vinyl ethyl ketone, vinyl isopropyl ketone, vinyln-butyl ketone, vinyl hexyl ketone, vinyl octyl ketone, methylisopropenyl ketone, vinyl aldehydes including acrolein, methacrolein,crotonaldehyde, vinyl ethers including vinyl methyl ether, vinyl ethylether, vinyl propyl ether, vinyl isobutyl ether, vinylidene compoundsincluding vinylidene chloride bromide, or bromochloride, also thecorresponding neutral or half-acid half-esters or free diacids of theunsaturated dicarboxylic acids including itaconic, citraconic, aconitic,fumaric, and maleic acids, substituted acrylamides, such as N-monoalkyl,—N,N-dialkyl-, and N-dialkylaminoalkylacrylamides or methacrylamideswhere the alkyl groups may have from one to eighteen carbon atoms, suchas methyl, ethyl, isopropyl, butyl, hexyl, cyclohexyl, octyl, dodecyl,hexadecyl and octadecyl aminoalkyl esters of acrylic or methacrylicacid, such as .beta.-dimethylaminoethyl, .beta.-diethylaminoethyl or6-dimethylaminohexyl acrylates and methacrylates, alkylthioethylmethacrylates and acrylates such as ethylthioethyl methacrylate,vinylpyridines, such as 2-vinylpyridine, 4-vinylpyridine,2-methyl-5-vinylpyridine, and so on.

In the case of copolymers containing ethylthioethyl methacrylate, theproducts can be oxidized to, if desired, the corresponding sulfoxide orsulfone.

Polyethylenically unsaturated monomers which ordinarily act as thoughthey have only one such unsaturated group, such as isoprene, butadiene,and chloroprene, may be used as part of the monoethylenicallyunsaturated category.

Examples of polyethylenically unsaturated compounds include:divinylbenzene, divinylpyridine, divinylnaphthalenes, diallyl phthalate,ethylene glycol diacrylate, ethylene glycol dimethacrylate,trimethylolpropanetrimethacrylate, divinylsulfone, polyvinyl orpolyallyl ethers of glycol, of glycerol, of pentaerythritol, ofdiethyleneglycol, of monothio or dithio-derivatives of glycols, and ofresorcinol, divinylketone, divinylsylfide, allyl acrylate, diallylmaleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallylmalonate, diallyl oxalate, diallyl adipate, diallyl sebacate, divinylsebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate,triallyl aconitate, triallyl citrate, triallyl phosphate,N,N′-methylenediacrylamide, N,N′-methylenedimethacrylamide,N,N′-ethylenediacrylamide, trivinylbenzene, trivinylnaphthalenes, andpolyvinylanthracenes.

A preferred class of monomers of this type is aromatic ethylenicallyunsaturated molecules such as styrene, vinyl pyridine, vinylnaphthalene, vinyl toluene, phenyl acrylate, vinyl xylenes, andethylvinylbenzene.

Examples of preferred polyethylenically unsaturated compounds includedivinyl pyridine, divinyl naphthalene, divinylbenzene, trivinylbenzene,alkyldivinylbenzenes having from 1 to 4 alkyl groups of 1 to 2 carbonatoms substituted in the benzene nucleus, and alkyltrivinylbenzeneshaving 1 to 3 alkyl groups of 1 to 2 carbon atoms substituted in thebenzene nucleus. Besides the homopolymers and copolymers of thesepoly(vinyl) benzene monomers, one or more of them may be copolymerizedwith up to 98% (by weight of the total monomer mixture) of (1)monoethylenically unsaturated monomers, or (2) polyethylenicallyunsaturated monomers other than the poly(vinyl)benzenes just defined, or(3) a mixture of (1) and (2). Examples of the alkyl-substituted di- andtri-vinyl-benzenes are the various vinyltoluenes, thedivinylethylbenzene, 1,4-divinyl-2,3,5,6-tetramethylbenzene,1,3,5-trivinyl-2,4,6-trimethylbenzene, 1,4-divinyl,2,3,6-triethylbenzene, 1,2,4-trivinyl-3,5-diethylbenzene,1,3,5-trivinyl-2-methylbenzene.

Most preferred are copolymers of styrene, divinylbenzene, andethylvinylbenzene.

Examples of suitable condensation monomers include: (a) aliphaticdibasic acids such as maleic acid, fumaric acid, itaconic acid,1,1-cyclobutanedicarboxylic acid, etc.; (b) aliphatic diamines such aspiperazine, 2-methylpiperazine, cis, cis-bis (4-aminocyclohexyl)methane, metaxylylenediamine, etc.; (c) glycols such as diethyleneglycol, triethylene glycol, 1,2-butanediol, neopentyl glycol etc.; (d)bischloroformates such as cis and trans-1,4-cyclohexyl bischloroformate,2,2,2,4-tetramethyl-1,3-cyclobutyl bischloroformate andbischloroformates of other glycols mentioned above, etc.; (e) hydroxyacids such as salicylic acid, m- and p-hydroxy-benzoic acid andlactones, derived therefrom such as the propiolactones, valerolactones,caprolactones, etc.; (f) diisocyanates such as cis andtrans-cyclopropane-1,2-diisocyanate, cis andtrans-cyclobutane-1-2-diisocyanate etc.; (g) aromatic diacids and theirderivatives (the esters, anhydrides and acid chlorides) such as phthalicacid, phthalic anhydride, terephthalic acid, isophthalic acid,dimethylphthalate, etc.; (h) aromatic diamines such as benzidine,4,4′-methylenediamine, bis(4-aminophenyl) ether, etc.; (i) bisphenolssuch as bisphenol A, bisphenol C, bisphenol F, phenolphthalein,recorcinol, etc.; (j) bisphenol bis(chloroformates) such as bisphenol Abis(chloroformate), 4,4′-dihydroxybenzophenone bis(chloroformate) etc.;(k) carbonyl and thiocarbonyl compounds such as formaldehyde,acetaldehyde, thioacetone acetone, etc.; (1) phenol and derivatives suchas phenol, alkylphenols, etc.; (m) polyfunctional cross-linking agentssuch as tri or poly basic acids such as trimellitic acid, tri or polyolssuch as glycerol, tri or polyamines such as diethylenetriamine; andother condensation monomers and mixtures of the foregoing.

Ion exchange resins produced from aromatic and/or aliphatic monomersprovide a preferred class of starting polymers for production of porousadsorbents. The ion exchange resin may also contain a functional groupselected from cation, anion, strong base, weak base, sulfonic acid,carboxylic acid, oxygen containing, halogen and mixtures of the same.Further, such ion exchange resins may optionally contain an oxidizingagent, a reactive substance, sulfuric acid, nitric acid, acrylic acid,or the like at least partially filling the macropores of the polymerbefore heat treatment.

The synthetic polymer may be impregnated with a filler such as carbonblack, charcoal, bonechar, sawdust or other carbonaceous material priorto pyrolysis. Such fillers provide an economical source of carbon whichmay be added in amounts up to about 90% by weight of the polymer.

The starting polymers, when ion exchange resins, may optionally containa variety of metals in their atomically dispersed form at the ionicsites. These metals may include iron, copper, silver, nickel, manganese,palladium, cobalt, titanium, zirconium, sodium, potassium, calcium,zinc, cadmium, ruthenium, uranium and rare earths such as lanthanum. Byutilizing the ion exchange mechanism it is possible for the skilledtechnician to control the amount of metal that is to be incorporated aswell as the distribution.

Although the incorporation of metals onto the resins is primarily to aidtheir ability to serve as catalytic agents, useful adsorbents may alsocontain metal.

Synthetic polymers, ion exchange resins whether in the acid, base ormetal salt form are commercially available. According to the inventionthere is also provided an adsorption process for separating componentsfrom a gaseous or liquid medium which comprises contacting the mediumwith particles of a pyrolyzed synthetic polymer.

For example it has been discovered that a styrenedivinylbenzene basedstrongly acidic exchange resin pyrolyzed from any of the forms ofHydrogen, Iron (III), Copper(II), Silver(I) or Calcium(II) can decreasethe concentration of vinylchloride in air preferably dry air frominitial concentration of 2 ppm to 300,000 ppm to a level of less than 1ppm at flow rates of 1 bedvolume/hour to 600 bedvolume/min. preferably10 to 200 bedvolume/minute.

The partially pyrolyzed macroporous polymer adsorbent of the presentinvention disclosed herein above are able to adsorb greater than 25 cm³STP of ethane per gram of sorbent at 35° C. and 200 mmHg of ethane andgreater than 30 cm³ STP of propane per gram of sorbent at 35° C. and 100mmHg of propane. Furthermore, these materials are able to be degassed ofethane or propane and then able to reabsorb greater than 25 cm³ STP ofethane per gram of sorbent at 35° C. and 200 mmHg of ethane, or reabsorbgreater than 30 cm³ STP of propane per gram of sorbent at 35° C. and 100mmHg of propane one or more times.

The separation process comprises passing a natural gas stream through anadsorber bed charged with the adsorbent(s) of the invention. Preferably,the ethane and/or propane and/or butane and/or pentane and/or heavierhydrocarbons, which are selectively adsorbed, can be readily desorbedeither by lowering the pressure or by increasing the temperature of theadsorber bed resulting in a regenerated adsorbent. The adsorbent soregenerated can be reused as an adsorbent for the separation of ethaneand/or propane and/or butane and/or pentane and/or heavier hydrocarbonsfrom the natural gas stream.

Batch, semi-continuous, and continuous processes and apparatuses forseparating NGLs from natural gas feedstreams are well known. FIG. 2depicts one embodiment of a separation process of the present invention.The separation unit 90 comprises an adsorption unit 10 and aregeneration unit 20. The separation process comprises the steps of (a)passing a natural gas feedstream 3 through an adsorption unit 10comprising an adsorbent bed 2 comprising an adsorbent media whichadsorbs heavier hydrocarbons (C₂, C₃, C₄, C₅, etc.) to obtain amethane-rich natural gas product 5 which may be compressed 100 andprovided to a natural gas pipeline 120 and/or for use as fuel for acombustion process, (b) transporting 11 adsorbent loaded with heavierhydrocarbons from the adsorption unit 10 to a regeneration unit 20comprising a means 32 to regenerate the loaded adsorbent media wherebyby causing the release of the heavier hydrocarbons 33 from the loadedadsorbing media and forming regenerated adsorbent media 23, (c) whereinthe regenerated adsorbent media 23 is transported 8 back to theadsorption unit 10 for reuse, and (d) the released heavier hydrocarbons33 are discharged 29, (e.g., recovered, excluded, by-passed, or flared)individually or as a mixture of gases (e.g., as C₂, C₃, C₄, C₅, etc.) orliquefied by a means 60, and recovered individually or as a mixtureliquids.

Although a particular preferred embodiment of the invention is disclosedin FIG. 2 for illustrative purposes, it will be recognized thatvariations or modifications of the disclosed process lie within thescope of the present invention. For example, in another embodiment ofthe present invention, there may be multiple adsorbent beds and/or theadsorbent bed(s) may be regenerated in-place as exemplified by U.S. Pat.No. 3,458,973, which is incorporated herein by reference in itsentirety.

The adsorption step and/or the regeneration step of the process of thepresent invention may operate in as a batch process, a semi-continuousprocess, a continuous process, or combination thereof. For instance inone embodiment of the present invention, both the adsorption step andthe regeneration step may operate in the batch mode. In anotherembodiment of the present invention both the adsorption step and theregeneration step may operate in the semi-continuous mode. In yetanother embodiment of the present invention both the adsorption step andthe regeneration step may operate in the continuous mode.

Alternatively, in one embodiment of the present invention the adsorptionstep may operate in a batch, semi-continuous, or continuous mode whilethe regeneration step operates in a different mode than that of theadsorption step. For example, in one embodiment of the present inventionthe adsorption step may operate in a batch mode while the regenerationstep operates in a continuous mode. In another embodiment of the presentinvention the adsorption step may operate in a continuous mode while theregeneration step operates in a continuous mode. All possiblecombinations of batch, semi-continuous, and continuous modes for theadsorbent step and regeneration step are considered within the scope ofthe present invention.

Adsorption is in many situations a reversible process. The practice ofremoving volatiles from an adsorption media can be accomplished byreducing the pressure over the media, heating, or the combination ofreduced pressure and heating. In either case the desired outcome is tore-volatilize the trapped vapors, and subsequently remove them from theadsorbent so that it can be reused to capture additional volatiles.Preferably, the adsorption media of the present invention whenregenerated, desorbs adsorbed gases in an amount equal to or greaterthan 75 percent of the amount adsorbed, more preferably equal to orgreater than 85 percent, more preferably equal to or greater than 90percent, more preferably equal to or greater than 95 percent, morepreferably equal to or greater than 99 percent and most preferablyvirtually all the NGLs adsorbed.

Traditional means of heating adsorbent media for the purpose of removingadsorbed volatiles that utilize conventional heating systems such asheated gas (air or inert gas), or radiant heat contact exchangers aresuitable for use in the present NGL separation process as part of theadsorbent media regeneration step.

Preferably, the NGL separation process of the present invention employsa microwave heating system as part of the adsorbent media regenerationstep. Such a microwave heating system provides a heating system andmethod for removing volatiles from adsorbent media with higher thermalefficiency at a reduced cost.

Referring to FIG. 3, a NGLs separation unit 90 comprises an adsorptionunit 10 which has an adsorption tank 1 containing an adsorbent bed 2comprising the adsorption media of the present invention. The naturalgas feedstream enters the adsorption unit 10 via line 3 at the lowerportion of the adsorption tank 1 and passes 4 through the adsorbent bed2. The adsorption bed 2 comprises an adsorbent media which can adsorbC₂, C₃, C₄, C₅, and heavier hydrocarbons from the natural gasfeedstream. Inlet temperature of the adsorption unit 10 can range from 5to 100° C., preferably from 15 to 80° C., and more preferably from 20 to70° C. Pressures of 14 to 1400 psia, preferably from 600 to 1200 psia,and more preferably from 800 to 1000 psia can be used. A methane-richnatural gas product stream a vastly reduced heavy hydrocarbon contentthan natural gas feedstream leaves the adsorbent bed 2 and is leavesfrom the top of the adsorption tank 1 through line 5. The methane-richnatural gas stream 5 may be compressed 100 and provided to a natural gaspipeline 120 and/or for use as fuel for a combustion process.

As the adsorption media becomes loaded with NGLs it passes through thebottom of the adsorption tank 1 through a transport mechanism 9 throughline 11 into a microwave regeneration unit 20 having a regeneration tank21 and a microwave heating system 32. The operating temperatures of themicrowave heating system 32 can range from 105 to 350° C., preferablyfrom 140 to 250° C., and more preferably from 145 to 200° C. Pressuresof from 20 to 600 psia, preferably 100 to 400 psia, and more preferably150 to 200 psia can be used. The microwave power source 30 heats theadsorbent media 2 in the microwave heating system 32 causing the NGLs tovaporize 33.

The microwave heating system 32 can irradiate a loaded adsorbent mediato desorb volatile materials. Irradiation of adsorbent media withmicrowave radiation can provide an economical and thermally efficientalternative for heating adsorbent materials to remove adsorbed volatilesfrom the adsorbent. Microwave radiation energy can be applied to anadsorbent without heating a gas, and can effectively transfer thermalenergy to specific adsorbents through path lengths in excess of 12inches. To accomplish this method of heating the adsorbent media, theapparatus for applying or generating the microwave radiation for aheating device must be constructed in such a manner as to afford uniformheating of the adsorbent, and to minimize or eliminate any reflection ofthe radiation back onto the microwave power source 30. The microwaveheating system 32 can include a heating apparatus and a heating orradiation system (not shown in FIG. 3), and optionally a purge gassystem 24. The heating apparatus can be coupled to and in communicationwith the radiation system for receipt of thermal energy generated by theradiation system, such as microwave radiation or electromagnetic energy,and with the purge gas system 24 for receipt of a purge gas to assist inthe removal of volatiles from the adsorbent.

The NGLs are extracted from the regeneration tank 21 through a suctionport 28 via a vacuum evacuation system 40. The regeneration tank 21 mayoptionally be fitted with a purge gas system 24 wherein purge gas, forexample nitrogen, enters through line 22 and is dispersed 25 at thebottom of the regeneration tank 21.

The regenerated adsorbent media 23 is allowed to pass from the bottom ofthe regeneration tank 21 through line 26 then returned to the adsorptiontank 1. A portion of the methane-rich natural gas from the top of theadsorber tank 1 is circulated via line 6 through blower 7 to transportthe regenerated adsorption media 23 through line 8 to once again adsorbNGLs from natural gas 3.

The NGLs vacuum extracted from the regeneration tank 21 pass through thevacuum extraction system 40 through a gas compression system 50 and partor all of the NGLs may be introduced into a condenser 60 where the NGLsare condensed, optionally separated, and discharged either as a mixtureof NGLs or individual fractions of ethane, propane, butane, pentane,and/or heavier hydrocarbons into one or more tank 73, 74, 75, and/or 76.The discharged NGLs may be recovered, transported, liquefied, excluded,by-passed, or flared. Any methane making it to the condenser is recycledback to the adsorption tank 1 through line 61 and any other gas(es),purge gas, water, and/or contaminants can be separated through line 62.

In one embodiment of the present invention, the NGL separation process90 is a continuous process with continuous adsorbent media regeneration.For example, in FIG. 3 there is a valve 12 in line 11 between theadsorber tank 1 and the regeneration tank 21 and a valve 27 in the line26 between the regeneration tank 21 and collection tank 17. Valves 12and 27 are synchronized to allow for holding loaded adsorption mediafrom the adsorption tank 1 while adsorption media is being regeneratedin the regenerator unit 20. When the adsorption media is regenerated inthe regenerator tank 21, valve 27 allows the regenerated adsorptionmedia 23 to leave the regenerator tank 21 and be transported back to theadsorption tank 1. Then valve 12 allows loaded adsorption media to enterthe regenerator tank 21 to be regenerated. This process is repeated andallows for a continuous regeneration of the adsorption media.

In another embodiment of the present invention, the NGL separationprocess 90 is a batch process with batch adsorbent media regeneration.For example, in FIG. 3 there is a holding tank 13 between the adsorptiontank 1 and the regeneration tank 21. When the adsorbent media 2 isloaded, all of it is conveyed from the adsorption tank 1 through thetransport mechanism 9 and line 11 to the holding tank 13. The contentsof the holding tank 13 are then transported through line 15 to theregeneration tank 21 where the loaded adsorbent media is regenerated andreturned to the adsorbent tank 1 where it is used until loaded and theprocess repeated.

Preferably the adsorbent used in the method of the present inventionwhen loaded with hydrocarbons, is regenerated using a microwaveregeneration system, for example as shown in FIG. 3. Preferably, themicrowave regeneration system is able to operate in a batch,semi-continuous, or continuous process. One advantage of using amicrowave system in conjunction with adsorbents of the present inventionis that it allows the microwaves to minimize the heating of the media,but maximize heating of the NGLs to encourage desorption. As such it hasthe benefits of being operationally simpler than traditionalregeneration systems, and reduces the heat effects on the adsorbentmaterial itself. Furthermore, when this desorption process is used inconjunction with a continuous adsorption process such as a moving packedbed or similar device, the hydrocarbon removal can be closely tailoredto the composition of the feed gas such that the recovered gas can haveimproved purity and, when present, reduced load on the subsequentchiller apparatus which allows for recovery and later transport as aliquid.

EXAMPLES

A description of the raw materials used in the Examples is as follows.

Example 1 is a porous cross-linked polymeric adsorbent having a highsurface area equal to or greater than 1,000 m²/g made from a macroporouscopolymer of a monovinyl aromatic monomer and a crosslinking monomer,where the macroporous copolymer has been post-crosslinked in the swollenstate in the presence of a Friedel-Crafts catalyst; Example 2 is aporous cross-linked polymeric adsorbent having a surface area equal toor greater than 1,000 m²/g made from a macroporous copolymer of amonovinyl aromatic monomer and a crosslinking monomer, where themacroporous copolymer has been post-crosslinked in the swollen state inthe presence of a Friedel-Crafts catalyst with post capping of residualchloromethyl groups with hydrophobic aromatic compounds resulting in amedia that has increased hydrophobicity; and Example 3 is a partiallypyrolized macroporous polymer of a monovinyl aromatic monomer and acrosslinking monomer that has been sulfonated.

Adsorption capacity and breakthrough properties are determined forExample 1 and Example 2 as followed:

Adsorption Capacity Methane, Ethane, Propane and Butane:

A Micromeritics ASAP 2020 Surface Area and Porosity Analyzer is used toanalyze methane (Sigma-Aldrich, 99.0%), ethane (Sigma-Aldrich, 99.99),propane (Sigma-Aldrich, 99.97%), and butane (Matheson Tri-Gas, 99.9%)adsorption at 308 K. Prior to analysis, the macroporous polymericadsorbent being tested (0.3 to 0.5 grams) is degassed in a quartz U-tubeat 423 K under vacuum to a pressure below 5 μmHg for 12 hours. Pressurepoints are taken between 5 to 600 mmHg with a 45 seconds equilibrationinterval. The samples are then evacuated under vacuum for 1 hour beforerepeating the pressure points.

Pentane:

A Micromeritics ASAP 2020 Surface Area and Porosity Analyzer equippedwith vapor introduction option with dual-zone temperature control isused to analyze static pentane adsorption at 273 K. An ethyleneglycol/water mixture contained within a chiller dewer is used astemperature control for the sample. Pentane (Sigma-Aldrich, anhydrous,≧99%) is placed in a quartz vessel located in the temperature-regulatedvapor furnace which is controlled to 308K. Prior to pentane analysis,the macroporous polymeric adsorbent being tested is degassed in a quartztube at 373 K under vacuum to a pressure below 5 μmHg for at least 12hours. Relative pressure points are taken between 0.005<P/P₀<0.50. Thesaturation pressure, P₀, was calculated to be 183.526 mmHg based onpentane adsorptive properties and the analysis bath temperature.

FIGS. 4 and 5 show the initial and repeat adsorption isotherms forbutane for Example 1 and Example 2, respectively.

FIG. 6 shows the initial and repeat adsorption isotherms for propane forExample 3.

FIGS. 7, 8, and 9 show the adsorption isotherms for ethane (C2), propane(C3), butane (C4), and pentane (C5) for Examples 1, 2, and 3,respectively.

Adsorption Breakthrough

Breakthrough curve data for the macroporous polymeric adsorbent isdetermined using a GC/mass spectrometer (mass spec). The GC/mass spec iscalibrated then a 40 g sample is loaded into the sample column. A mixedgas comprising a ratio of CH₄/C₂H₆/C₃H₈/C4H₁₀ at 40/40/40/40 standardcubic centimeters per minute (SCCM) is analyzed. Gas flow is initiated.This flow by-passes the packed bed (i.e., column). The system is allowedto equilibrate for 2 hours. The gas from the by-pass is then analyzed bythe mass spec. Following a two minute delay, the three-way valve isopened to allow the mixed gas to enter the packed bed column. The datafor the mass spec analysis of the mixed gas leaving the packed bedcolumn is recorded. The system is allowed to run until all four gaseshave been analyzed in the mass spec and recorded. Table 1 lists thebreakthrough times for each gas.

TABLE 1 Polymeric Sorbent Media Example 1 Example 2 Example 3 Weight, g40 40 40 Volume, cc 109 130 71 Bulk Density, g/cc 0.37 0.31 0.56 Methanebreakthrough, min 5.2 6 6.3 Ethane breakthrough, min 13.2 16.5 11.1Propane Breakthrough, min 27.3 33.2 16.4 Butane breakthrough, min 6481.4 31.9

What is claimed is:
 1. A method to remove and recover some or all of thenatural gas liquids (NGLs): ethane, propane, butane, pentane, or heavierhydrocarbons, from a natural gas feedstream to provide a methane-richnatural gas supply wherein the NGLs are separated from the natural gasfeedstream by means of a NGLs separation unit comprising: (i) anadsorption unit comprising an adsorption bed comprising an adsorbentmedia which adsorbs NGLs to form a loaded adsorbent media and (ii) aregeneration unit comprising a means to regenerate loaded adsorbentmedia by causing the release of adsorbed NGLs from the loaded adsorbingmedia and forming regenerated adsorbent media wherein the methodcomprises the steps of: (a) passing the natural gas feedstream throughthe adsorption unit generating the adsorbent loaded with NGLs and amethane-rich natural gas supply, (b) transporting the adsorbent loadedwith NGLs from the adsorption unit to the regeneration unit, (c)regenerating the adsorbent loaded with NGLs by releasing the adsorbedNGLs from the loaded adsorbing media and forming regenerated adsorbentmedia (d) transporting the regenerated adsorbent media back to theadsorption unit for reuse, (e) recovering the released NGLs, and (f)providing the methane-rich natural gas supply to a natural gas pipelinefor transportation and/or for use as fuel for a combustion process. 2.The method of claim 1 wherein the source of the natural gas feedstreamis from an oil well, a gas well, a condensate well, or a pipelinenatural gas containing NGLs.
 3. The method of claim 1 wherein themethane-rich natural gas supply has a BTU value equal to or less than1073.
 4. The method of claim 1 wherein the adsorption media is silicagel, alumina, silica-alumina, zeolites, activated carbon, polymersupported silver chloride, copper-containing resins, porous cross-linkedpolymeric adsorbents, pyrolized macroporous polymers, or mixturesthereof.
 5. The method of claim 1 wherein the adsorption media is aporous cross-linked polymeric adsorbent, a pyrolized macroporouspolymer, or mixtures thereof.
 6. The method of claim 1 wherein theloaded adsorption media is regenerated by means of reduced pressure overthe media, heating the media, or a combination of reduced pressure andheating.
 7. The method of claim 1 wherein the loaded adsorption media isregenerated by a microwave heating system.
 8. The method of claim 1wherein the regeneration step is operated as a batch process, asemi-continuous process, or as a continuous process.
 9. The method ofclaim 1 further comprising the step (g) transporting the recovered NGLsby pipeline, truck, rail, or ship to a chemical processing facilitywhere one or more of the NGLs is used as a chemical feedstock in thechemical processing facility.